ASYMMETRIC SYNTHESIS OF 1,3-POLYOLS VIA HYDROSILATION

本研究探索了一种通过高烯丙醇分子内硅氢化合成1，3-二醇和1，3，5-三醇官能团的新方法。烯烃表面选择性是通过使用连接到起始材料的硅原子上的手性助剂(AC2对称联萘酚)来提供的。建议在后续的转化中，手性助剂将能够进一步用于在整个产品中传递立体化学信息。因此，通过进一步的官能化和操作，应该生产1，3-多元醇官能团。在这种情况下，提出了手性助剂可以控制三个中心的绝对立体化学，然后从产品中裂解和回收。1，3-多元醇的重要性源于它们在天然产品世界中的广泛存在。几种抗生素、抗肿瘤和免疫抑制化合物都含有这种功能。一种这样的化合物，(-)discodermolide，含有三个1，3，5-三醇单元，其中一个应该可以用拟议的方法获得。为了进一步探索硅系留方法的范围，建议所有三个构造块都使用氢硅化方法的变体来制造，并且在使天然产物的主链使用硅系链烯环闭合复分解反应协议进行的过程中是一个重要的连接。

The proposed research explores a novel methodology for the synthesis of 1,3-diol and 1,3,5-triol functionalities via the intramolecular hydrosilation of homoallylic alcohols. Alkene facial selectivity is afforded by the use of a chiral auxiliary (aC2 symmetric binaphthol) attached to the silicon atom of the starting material. It is proposed that the chiral auxiliary will then be able to be further utilized in relaying stereochemical information throughout the product in subsequent transformations. Thus through further functionalization and manipulation 1,3-polyol functionalities should be produced. In such a way, it is proposed that the chiral auxiliary can control the absolute stereochemistry of three centers before being cleaved from the product and recycled. The importance of 1,3-polyols is born out in their vast presence in the natural product world. Several antibiotic, anti-tumor and immunosuppressant compounds contain this functionality. One such compound, (-) discodermolide, contains three 1,3,5-triol units, one of which should be accessible using the proposed methodology. To further explore the scope of silicon tethered methodology, it is proposed that all three building blocks be made using variations of the hydrosilation methodology, and an important connection in making the backbone of the natural product be performed using a silicon tethered alkene ring closing metathesis protocol.